DE60017612T2 - AZEOTROP-SIMILAR COMPOSITIONS AND THEIR USE - Google Patents

Abstract

The invention provides azeotrope-like compositions consisting essentially of RfCF(OC2H5)CF(CF3)2, where Rf is a straight chain perfluoroalkyl group having 3 carbon atoms, and an organic solvent selected from the group consisting of: (a) unsubstituted straight chain, branched chain, and cyclic saturated alkanes containing 8 to 11 carbon atoms; (b) chlorinated straight chain, branched chain, and cyclic saturated alkanes containing 5 to 7 carbon atoms; (c) aromatic or unsaturated cyclic halogenated or unhalogenated hydrocarbons containing 7 to 10 carbon atoms; (d) esters containing 6 carbon atoms; (e) ketones containing 6 to 7 carbon atoms; (f) glycol ethers containing 6 carbon atoms; and (g) siloxanes containing 8 carbon atoms.

Description

The The invention relates to azeotropes, azeotrope-like compositions and Methods in which azeotropes and azeotrope-like compositions for Cleaning substrates, depositing coatings, transferring of heat energy and used as a reactant medium.

Chlorofluorocarbons (CFC), chlorofluorocarbons (CFCs) and chlorinated hydrocarbons (CHC, e.g. 1,1,1-trichloroethane and carbon tetrachloride) are already extensive Range of different solvent applications such as drying, cleaning (e.g., removal of flux residues of printed circuits) and vapor degreasers. Such materials have also been used in cooling and heat transfer processes Service. Although these materials initially considered environmentally friendly they are now linked to ozone depletion. In accordance with the Montreal Protocol and its addendums, the Production and use of CFRP find an end (compare e.g. P. S. Zurer, "Looming Ban on Production of CFCs, Halon's Spurs Switch to Substitutes "(threatening ban the production of CFRP, halons boost the transition to replacement products on), Chemical & Engineering News, page 12, 15 November 1993). The characteristic properties, the additional to a low ozone depletion potential in the replacement products are typically boiling ranges that are required for a series various solvent cleaning applications suitable, low flammability and low toxicity includes. Solvent substitutes should also have the ability own, dirt types both on the basis of hydrocarbons as well as hydrofluorocarbons. Preferably, solvent substitutes also a low toxicity, no flash point (measured according to ASTM D3278-89), an acceptable Stability, short lifetimes in the atmosphere and a low global one warming potential on.

Certain perfluorinated (PFK) and highly fluorinated fluorocarbon (HFC) materials are as CFK and CFRP substitutes for Solvent applications been evaluated. While these materials are generally sufficiently chemically resistant, not toxic and non-flammable to be used in solvent applications the PFK tend to be persistent in the atmosphere and PFK and HFCs are generally less effective than CFCs and CFCs in hydrocarbon materials to solve or to disperse. Also, blends of PFK or HFC with others organic solvents generally better solvents and dispersants for Hydrocarbons as PFK or HFC as such.

hydrofluoroether (HFE) or strongly fluorinated ethers are also of interest Substitutes for FCK and CFCs attracted. HFE are also chemically resistant a low toxicity are not flammable and not ozone depleting. segregated HFE, a subclass of HFE, in which all fluorine atoms on one Side of and / or segregated between the ether oxygen atom (s) generally have the additional advantage that they are very much compared to many of their non-segregated HFE counterparts short lifetimes in the air (typically less than 5 years and even as little as 0.77 years). However, as with the PFK and HKW auxiliary solvent with hydrocarbons to improve solubility and dispersibility he wishes.

Many azeotropes have properties that make them useful solvents. For example, azeotropes have a constant boiling point, thereby avoiding a boiling temperature shift during processing and use. In addition, when an azeotrope is used as a solvent, the properties of the solvent remain constant because the composition of the solvent does not change during boiling or reflux cooling. Azeotropes used as solvents can also conveniently be recovered by distillation. For relatively low boiling (boiling below 80 ° C) segregated HFE such as C ₄ F ₉ OCH ₃ , C ₄ F ₉ OC ₂ H ₅ and C ₃ F ₇ OCH ₃ are useful azeotropic and azeotrope-like compositions with hydrocarbon or chlorinated hydrocarbon Solvents such as paraffinic hydrocarbons, alcohols and chlorinated ethylene have been identified. However, no azeotropic or azeotrope-like compositions have been identified hitherto containing higher boiling segregated HFE. Higher boiling HFEs are suitable for removing deposits requiring high temperature softening, such as waxes, high viscosity lubricants, but higher boiling HFEs are generally relatively poor solvents when used as such.

There is therefore a need for azeotropic or azeotrope-like compositions which can replace higher boiling chlorine-containing solvents such as trichloroethane, carbon tetrachloride, trichlorethylene and perchlorethylene. Preferably, these compositions are non-flammable, have a good dissolving power, are not ozone-depleting and have a relatively short life in the air, so that they do not contribute significantly to warming the atmosphere.

The present invention provides azeotropes and azeotrope-like ones Compositions of a higher boiling segregated HFE. These compositions are preferably non-flammable, have a good solvent power, are not ozone depleting and have a relatively short life the air.

In one embodiment, the present invention provides azeotrope and azeotrope-like compositions consisting essentially of a hydrofluoroether and an organic solvent. The hydrofluoroether, namely 3-ethoxyperfluoro (2-methylhexane), is represented by the general formula R _f CF (OC ₂ H ₅ ) CF (CF ₃ ) ₂ where R _{f is} a straight chain perfluoroalkyl group having 3 carbon atoms. The organic solvent is selected from the group consisting of: (a) 8 to 11 carbon atoms containing unsubstituted straight-chain, branched-chain and cyclic saturated alkanes; (b) chlorinated straight, branched and cyclic saturated alkanes containing from 5 to 7 carbon atoms; (c) from 7 to 10 carbon atoms containing aromatic or unsaturated cyclic halogenated or non-halogenated hydrocarbons; (d) esters containing 6 carbon atoms; (e) ketones containing 6 to 7 carbon atoms; (f) glycol ethers containing 6 carbon atoms; (g) siloxanes containing 8 carbon atoms.

While the Concentrations of the hydrofluoric ether and the organic solvent, those in the azeotrope-like Composition are included, to a degree, by the Concentrations may differ which are to be found in the azeotrope formed between them, are the boiling points of the azeotrope-like compositions essentially the same as those of their corresponding ones Azeotropes. Preferably, the azeotrope-like compositions boil at ambient pressure at temperatures within about 1 ° C of the temperatures lie where their corresponding azeotropes at the same pressure boil. Thus, the azeotrope-like compositions of the invention comprise the corresponding azeotrope.

at another embodiment, the present invention provides a Method for cleaning objects by contacting the object to be cleaned with one or more of the azeotrope-like ones Compositions of the invention or the vapor of such compositions, until undesirable impurities or types of spoils on the object dissolved, dispersed or displaced and washed away are.

at yet another embodiment, the present invention provides a method for coating substrates with the aid of the azeotrope-like Compositions as solvents or carrier for the Coating material. The method includes the step of giving up on at least a part of at least one surface of a A coating composition substrate comprising: (a) an azeotrope-like one Composition; and (b) at least one coating material, the in the azeotrope-like Composition soluble or dispersible. Preferably, the method further comprises the Step of removing the azeotrope-like composition of the coating composition, for example by evaporation.

The The present invention also provides coating compositions comprising an azeotrope-like Composition and coating material used in the coating process are useful.

at yet another embodiment, the present invention provides a method for transmitting Thermal energy with the help of azeotrope-like Composition as heat transfer fluids.

at In yet another embodiment, the invention provides a method for preparing a desired organic compound by reacting one or more reactants in a reaction medium consisting essentially of the inventive azeotrope-like compositions

1 Figure 9 is a plot of boiling point versus concentration of C ₃ F ₇ CF (OC ₂ H ₅ ) CF (CF ₃ ) ₂ and 2-heptanone. Points A and B indicate the endpoints for the azeotrope-like composition.

2 shows a graphical representation of the boiling point as a function of the concentration of C ₃ F ₇ CF (OC ₂ H ₅₎ CF (CF _{3) 2} and ISOPAR ^™ G. Points A and B indicate the endpoints for the azeotrope-like composition.

3 Figure ₁₀ is a graph of boiling point versus concentration of C ₃ F ₇ CF (OC ₂ H ₅ ) CF (CF ₃ ) ₂ and p-chlorobenzotrifluoride. Points A and B indicate the endpoints for the azeotrope-like composition.

4 Figure ₁₀ is a graph of boiling point versus concentration of C ₃ F ₇ CF (OC ₂ H ₅ ) CF (CF ₃ ) ₂ and alpha-pinene. Points A and B indicate the endpoints for the azeotrope-like composition.

5 Figure 9 shows a plot of boiling point versus concentration of C ₃ F ₇ CF (OC ₂ H ₅ ) CF (CF ₃ ) ₂ and beta-pinene. Points A and B indicate the endpoints for the azeotrope-like composition.

6 Figure ₁₀ is a graph of boiling point versus concentration of C ₃ F ₇ CF (OC ₂ H ₅ ) CF (CF ₃ ) ₂ and 1-chloro-n-heptane. Points A and B indicate the endpoints for the azeotrope-like composition.

7 Figure 9 is a plot of boiling point versus concentration of C ₃ F ₇ CF (OC ₂ H ₅ ) CF (CF ₃ ) ₂ and octamethyltrisiloxane. Points A and B indicate the endpoints for the azeotrope-like composition.

8th Figure 9 is a graph of boiling point versus concentration of C ₃ F ₇ CF (OC ₂ H ₅ ) CF (CF ₃ ) ₂ and m-xylene. Points A and B indicate the endpoints for the azeotrope-like composition.

9 Figure 9 is a plot of boiling point versus concentration of C ₃ F ₇ CF (OC ₂ H ₅ ) CF (CF ₃ ) ₂ and 1-chloro-n-hexane. Points A and B indicate the endpoints for the azeotrope-like composition.

10 Figure 9 is a plot of boiling point versus concentration of C ₃ F ₇ CF (OC ₂ H ₅ ) CF (CF ₃ ) ₂ and n-butyl acetate. Points A and B indicate the endpoints for the azeotrope-like composition.

11 Figure 9 is a plot of boiling point versus concentration of C ₃ F ₇ CF (OC ₂ H ₅ ) CF (CF ₃ ) ₂ and n-octane. Points A and B indicate the endpoints for the azeotrope-like composition.

12 Figure ₁₀ is a plot of boiling point versus concentration of C ₃ F ₇ CF (OC ₂ H ₅ ) CF (CF ₃ ) ₂ and n-propyl n-propionate. Points A and B indicate the endpoints for the azeotrope-like composition.

13 Figure 9 is a graph of boiling point versus concentration of C ₃ F ₇ CF (OC ₂ H ₅ ) CF (CF ₃ ) ₂ and 1,3-dimethylcyclohexane. Points A and B indicate the endpoints for the azeotrope-like composition.

14 Figure 9 is a plot of boiling point versus concentration of C ₃ F ₇ CF (OC ₂ H ₅ ) CF (CF ₃ ) ₂ and methyl isobutyl ketone. Points A and B indicate the endpoints for the azeotrope-like composition.

15 Figure 9 is a plot of boiling point versus concentration of C ₃ F ₇ CF (OC ₂ H ₅ ) CF (CF ₃ ) ₂ and isobutyl acetate. Points A and B indicate the endpoints for the azeotrope-like composition.

16 Figure 9 is a plot of boiling point versus concentration of C ₃ F ₇ CF (OC ₂ H ₅ ) CF (CF ₃ ) ₂ and toluene. Points A and B indicate the endpoints for the azeotrope-like composition.

17 shows a graphical representation of the boiling point as a function of the concentration of C ₃ F ₇ CF (OC ₂ H ₅ ) CF (CF ₃ ) ₂ and 1-chloro-n-pentane. Points A and B indicate the endpoints for the azeotrope-like composition.

18 Figure 9 is a plot of boiling point versus concentration of C ₃ F ₇ CF (OC ₂ H ₅ ) CF (CF ₃ ) ₂ and diglyme. Points A and B indicate the endpoints for the azeotrope-like composition.

Precise description the illustrative embodiments

A Azeotropic composition or an azeotrope is a liquid mixture with constant boiling point of two or more substances that behaves like a single substance, by the one by partial Vaporizing the liquid Steam produced at its boiling point has the same composition like the liquid having. Azeotropic compositions are mixtures of consistent Boiling point, which is either a maximum or a minimum boiling point in comparison with other composition have the same substances.

A Azeotropelike Composition contains the corresponding azeotrope. Inventive azeotrope-like Composition are mixtures of hydrofluoroether and organic Solvents that, with the aid of simple distillation (i.e. a bottom-up distillation), a distillate fraction form an azeotrope of hydrofluoroether and organic solvent is.

The azeotrope-like compositions boil at temperatures substantially the same as the boiling points of their corresponding azeotrope. Preferably, the boiling point of an azeotrope-like composition at ambient pressure is within about 1 ° C of the boiling point of its azeotrope, measured at the same pressure. Compare the figures. Note that for ISOPAR ^™ G, the boiling point of an azeotrope-like composition at ambient pressure is within about 0.4 ° C of the boiling point of its azeotrope, measured at the same pressure. Compare 2 ,

The Concentration of the hydrofluoroether and organic solvent in a specific azeotrope-like Composition may be significantly different from the corresponding azeotropic Composition and the extent of such allowable variation depends on the organic solvent. Most preferably the azeotrope-like Composition essentially the same concentrations Ethers and solvents, as contained in the azeotrope, between them at ambient pressure is formed. The concentrations of ether and organic go away solvent in the azeotrope-like Composition of the concentrations in the corresponding Azeotrope are included, so contain the preferred compositions a concentration of ether that determines the concentration of the ether in the azeotrope. Such compositions are likely to be less flammable as azeotrope-like Compositions in which the organic solvent in a concentration present, which exceeds their concentration in the azeotrope. The most preferred Compositions show no significant change in solvent power Composition over time.

The Azeotrope-like according to the invention Compositions can also in addition to the hydrofluoroether and the organic solvent small amounts Other compounds that do not contain the formation of the azeotrope to disturb. For example, you can low levels of surfactants in the azeotrope-like compositions of the present invention for improving the dispersibility or solubility of materials such as Water, soils or coating materials (e.g., perfluoropolyether lubricants and Fluoropolymers) in the azeotrope-like Composition present.

hydrofluoroether

The hydrofluoroether 3-ethoxyperfluoro (2-methylhexane) of the present invention can be represented by the following general formula R _f CF (OC ₂ H ₅₎ CF (CF _{3) 2} (I) in the above formula, R _{f is} a straight-chain (ie, linear) perfluoroalkyl group having 3 carbon atoms.

3-Ethoxyperfluoro (2-methylhexane), nC ₃ F ₇ CF (OC ₂ H ₅ ) CF (CF ₃ ) ₂ can be used as an extremely pure product on be can be prepared by using a two-step reaction to first produce a perfluorinated ketone, namely perfluoro (2-methyl-3-hexanone) of the structure nC ₃ F ₇ C (O) CF (CF ₃ ) ₂ , which in turn donates with an ethyl group Alkylating agent is alkylated to obtain the desired secondary ether. Perfluoro (2-methyl-3-hexanone) can be prepared by reacting perfluoro (n-propyl) carbonyl fluoride (nC ₃ F ₇ COF, minimum purity 85 percent) with hexafluoropropylene (CF ₂ = CFCF ₃ ) in the presence of an anhydrous fluoride ion donor in an anhydrous polar aprotic solvents are prepared in a pressurized reaction vessel such as a Parr reactor at a temperature of about 70 ° C for about 3 hours. Suitable anhydrous fluoride ion donors include anhydrous alkali metal fluoride (eg, potassium fluoride or cesium fluoride) or anhydrous silver fluoride; Anhydrous potassium fluoride (spray dried, stored at 125 ° C, ground to a granulated powder shortly before use) is preferred. Suitable anhydrous polar aprotic solvents include acyclic ethers such as diethyl ether, ethylene glycol dimethyl ether (glyme) and diethylene glycol dimethyl ether (diglyme); Carboxylic acid esters such as methyl formate, ethyl formate, methyl acetate, diethyl carbonate, propylene carbonate and ethylene carbonate; Alkylnitriles such as acetonitrile; Alkylamides such as N, N-dimethylformamide, N, N-diethylformamide and N-methylpyrrolidone; Alkyl sulfoxides such as dimethylsulfoxide; Alkylsulfone such as dimethylsulfone; Tetramethylene sulfones and other sulfolanes; Oxazolidones such as N-methyl-2-oxazolidone; and mixtures thereof; Preferably, the polar aprotic solvent is diethylene glycol dimethyl ether (diglyme).

Then, a slight molar excess of an ethyl group donating alkylating agent and a quaternary ammonium salt such as triallylmonomethylammonium halide (eg, ADOGEN ^™ 464, available from Witco Corp. Oleo / Surfactant Group, Greenwich, CT) with the perfluoro (2-methyl-3 hexane) and the resulting mixture is heated to about 50 ° C for about 3 days with maximum stirring. Suitable ethyl group donating alylating agents include diethyl sulfate, ethyl iodide, ethyl p-toluenesulfonate and ethyl perfluoromethyl sulfonate; Diethyl sulfate is the preferred alkylating agent. The reactor is then charged with aqueous alkali, eg potassium hydroxide, and heated to about 85 ° C for about 1½ hours. The reactor contents are then distilled to give a crude product containing about 85-90 percent 3-ethoxy-perfluoro (2-methylhexane).

The Crude product is (for example, with the aid of a jacketed Oldershaw vacuum column with 10 floors) fractionated, washed with water and dried over a desiccant (such as for example, anhydrous magnesium sulfate). The NMR analysis of the purified product typically indicates purity fractionating greater than 99.7 percent of 3-ethoxy-perfluoro (2-methylhexane) with a isomeric purity of more than 95 percent.

General Preparation methods for the ethers are also in French Patent No. 2,287,432 and German Patent No. 1,294,949.

The perfluorinated acyl fluoride (for use in preparing the hydrofluoroether) can by electrochemical fluorination (ECF) of the corresponding Hydrocarbon carboxylic acid (or a derivative thereof) with the help of either anhydrous hydrogen fluoride (Simons ECF) or KF-2HF (Phillips ECF) be prepared as an electrolyte. The perfluorinated acyl fluoride and perfluorinated ketone can also be obtained by dissociation of a perfluorinated carboxylic acid ester (From the corresponding hydrocarbon or partially fluorinated Carbonsäureester prepared by direct fluorination with fluorine gas) become.

The Dissociation can also be achieved by contacting the perfluorinated ester with a fluoride ion source under reaction conditions (compare U.S. Patent No. 3,900,373 (Childs) and U.S. Pat. 5,466,877 (Moore)) or by combining of the ester with at least one initiator reagent selected from the group selected is made up of gaseous Nonhydroxylnucleophiles, liquid Non-hydroxyl nucleophiles and mixtures of at least one nonhydroxyl neuropil (Gaseous, aqueous or solid) and at least one solvent, the acylating agents towards inert is to be achieved.

organic solvent

The organic solvents of the present invention include: (a) n-octane, 1,3-dimethylcyclohexane, and ISOPRR ^™ G, which is a mixture of very low aromatic content C ₁₀ -C ₁₁ isoparaffinic hydrocarbons available from Exxon Chemical Co. Houston, TX; (b) 1-chloro-n-pentane, 1-chloro-n-hexane and 1-chloro-n-heptane; (c) toluene, m-xylene, α-pinene, β-pinene and p-chlorobenzotrifluoride; (d) n-butyl acetate, isobutyl acetate and n-propyl n-propionate; (e) methyl isobutyl ketone and 2-Hep tanon; (f) diethylene glycol dimethyl ether (diglyme); and (g) octamethyltrisiloxane.

• (i) Zusammensetzungen bestehend im Wesentlichen aus 86 bis 41 Gewichtsprozent 3-Ethyoxyperfluor(2-methylhexan) und 14 bis 59 Gewichtsprozent n-Octan, die bei 115.5 bis 116,5°C bei ca. 1 bar (760 Torr) sieden;
• (ii) Zusammensetzungen bestehend im Wesentlichen aus 79 bis 32 Gewichtsprozent 3-Ethyoxyperfluor(2-methylhexan) und 21 bis 68 Gewichtsprozent 1,3-Diemthylcyclohexan, die bei 112,0 bis 113,0°C bei ca. 1 bar (760 Torr) sieden;
• (iii) Zusammensetzungen bestehend im Wesentlichen aus 99,9 bis 89 Gewichtsprozent 3-Ethyoxyperfluor(2-methylhexan) und 0,1 bis 11 Gewichtsprozent ISOPAR^TMG, die bei 129,7 bis 130,1°C bei ca. 1 bar (760 Torr) sieden;
• (iv) Zusammensetzungen bestehend im Wesentlichen aus 74 bis 20 Gewichtsprozent 3-Ethyoxyperfluor(2-methylhexan) und 26 bis 80 Gewichtsprozent 1-Chlor-n-pentan, die bei 103,8 bis 104,8°C bei ca. 1 bar (760 Torr) sieden;
• (v) Zusammensetzungen bestehend im Wesentlichen aus 89 bis 55 Gewichtsprozent 3-Ethyoxyperfluor(2-methylhexan) und 11 bis 45 Gewichtsprozent 1-Chlor-n-hexan, die bei 120,1 bis 121,1°C bei ca. 1 bar (760 Torr) sieden;
• (vi) Zusammensetzungen bestehend im Wesentlichen aus 98 bis 68 Gewichtsprozent 3-Ethyoxyperfluor(2-methylhexan) und 2 bis 32 Gewichtsprozent 1-Chlor-n-heptan, die bei 128,0 bis 129,0°C bei ca. 1 bar (760 Torr) sieden;
• (vii) Zusammensetzungen bestehend im Wesentlichen aus 76 bis 24 Gewichtsprozent 3-Ethyoxyperfluor(2-methylhexan) und 24 bis 76 Gewichtsprozent Toluol, die bei 105,1 bis 106,1°C bei ca. 1 bar (760 Torr) sieden;
• (viii) Zusammensetzungen bestehend im Wesentlichen aus 91 bis 58 Gewichtsprozent 3-Ethyoxyperfluor(2-methylhexan) und 9 bis 42 Gewichtsprozent m-Xylol, die bei 122,3 bis 123,3°C bei ca. 1 bar (760 Torr) sieden;
• (ix) Zusammensetzungen bestehend im wesentlichen aus 96 bis 65 Gewichtsprozent 3-Ethyoxyperfluor(2-methylhexan) und 4 bis 35 Gewichtsprozent α-Pinen, die bei 127,1 bis 128,1°C bei ca. 1 bar (760 Torr) sieden;
• (x) Zusammensetzungen bestehend im Wesentlichen aus 99,7 bis 77 Gewichtsprozent 3-Ethyoxyperfluor(2-methylhexan) und 0,3 bis 23 Gewichtsprozent β-Pinen, die bei 128,8 bis 129,8°C bei ca. 1 bar (760 Torr) sieden;
• (xi) Zusammensetzungen bestehend im Wesentlichen aus 91 bis 52 Gewichtsprozent 3-Ethyoxyperfluor(2-methylhexan) und 9 bis 48 Gewichtsprozent p-Chlorbenzotrifluorid, die bei 126,8 bis 127,8°C bei ca. 1 bar (760 Torr) sieden;
• (xii) Zusammensetzungen bestehend im Wesentlichen aus 83 bis 36 Gewichtsprozent 3-Ethyoxyperfluor(2-methylhexan) und 17 bis 64 Gewichtsprozent n-Butylacetat, die bei 117,6 bis 118,6°C bei ca. 1 bar (760 Torr) sieden;
• (xiii) Zusammensetzungen bestehend im Wesentlichen aus 73 bis 23 Gewichtsprozent 3-Ethyoxyperfluor(2-methylhexan) und 27 bis 77 Gewichtsprozent Isobutylacetat, die bei 112,2 bis 113,2°C bei ca. 1 bar (760 Torr) sieden;
• (xiv) Zusammensetzungen bestehend im Wesentlichen aus 80 bis 31 Gewichtsprozent 3-Ethyoxyperfluor(2-methylhexan) und 20 bis 69 Gewichtsprozent n-Propyl-n-propionat, die bei 115,7 bis 116,7°C bei ca. 1 bar (760 Torr) sieden;
• (xv) Zusammensetzungen bestehend im Wesentlichen aus 73 bis 24 Gewichtsprozent 3-Ethyoxyperfluor(2-methylhexan) und 27 bis 76 Gewichtsprozent Methylisobutylketon, die bei 110,9 bis 111,9°C bei ca. 1 bar (760 Torr) sieden;
• (xvi) Zusammensetzungen bestehend im Wesentlichen aus 96 bis 69 Gewichtsprozent 3-Ethyoxyperfluor(2-methylhexan) und 4 bis 31 Gewichtsprozent 2-Heptanon, die bei 127,7 bis 128,7°C bei ca. 1 bar (760 Torr) sieden;
• (xvii) Zusammensetzungen bestehend im Wesentlichen aus 99,9 bis 75 Gewichtsprozent 3-Ethyoxyperfluor(2-methylhexan) und 0,1 bis 25 Gewichtsprozent Diethylenglykoldimethylether (Glyme), die bei 128,9 bis 129,9°C bei ca. 1 bar (760 Torr) sieden;
• (xviii) Zusammensetzungen bestehend im Wesentlichen aus 96 bis 67 Gewichtsprozent 3-Ethyoxyperfluor(2-methylhexan) und 4 bis 33 Gewichtsprozent Octamethyltrisiloxan, die bei 127,4 bis 128,4°C bei ca. 1 bar (760 Torr) sieden;

Azeotrope-like compositions containing 3-ethoxyperfluoro (2-methylhexane) and the organic solvents listed above include the following:

• (i) compositions consisting essentially of 86 to 41 percent by weight of 3-ethoxy-perfluoro (2-methylhexane) and 14 to 59 percent by weight of n-octane boiling at 115.5 to 116.5 ° C at about 1 bar (760 torr);
• (ii) Compositions consisting essentially of 79 to 32 weight percent of 3-ethoxy-perfluoro (2-methylhexane) and 21 to 68 weight percent of 1,3-dimethylcyclohexane prepared at 112.0 to 113.0 ° C at about 1 bar (760 torr ) boil;
• (iii) Compositions consisting essentially of 99.9 to 89 weight percent of 3-ethoxy-perfluoro (2-methylhexane) and 0.1 to 11 weight percent of ISOPAR ^™ G, which at 129.7 to 130.1 ° C at about 1 bar ( 760 Torr);
• (iv) Compositions consisting essentially of 74 to 20% by weight of 3-ethoxy-perfluoro (2-methylhexane) and 26 to 80% by weight of 1-chloro-n-pentane, which at 103.8 to 104.8 ° C at about 1 bar ( 760 Torr);
• (v) Compositions consisting essentially of 89 to 55 percent by weight of 3-ethoxy-perfluoro (2-methylhexane) and 11 to 45 percent by weight of 1-chloro-n-hexane, which at 120.1 to 121.1 ° C at about 1 bar ( 760 Torr);
• (vi) Compositions consisting essentially of 98 to 68 weight percent 3-Ethyoxyperfluor (2-methylhexane) and 2 to 32 weight percent 1-chloro-n-heptane, which at 128.0 to 129.0 ° C at about 1 bar ( 760 Torr);
• (vii) compositions consisting essentially of 76 to 24 weight percent 3-ethoxy-perfluoro (2-methylhexane) and 24 to 76 weight percent toluene boiling at 105.1 to 106.1 ° C at about 1 bar (760 torr);
• (viii) compositions consisting essentially of 91 to 58 weight percent of 3-ethoxy-perfluoro (2-methylhexane) and 9 to 42 weight percent of m-xylene boiling at 122.3 to 123.3 ° C at about 1 bar (760 Torr) ;
• (ix) Compositions consisting essentially of 96 to 65 weight percent of 3-ethoxy-perfluoro (2-methylhexane) and 4 to 35 weight percent of α-pinene boiling at 127.1 to 128.1 ° C at about 1 bar (760 torr) ;
• (x) compositions consisting essentially of 99.7 to 77 weight percent of 3-ethoxy-perfluoro (2-methylhexane) and 0.3 to 23 weight percent of β-pinene, which at 128.8 to 129.8 ° C at about 1 bar ( 760 Torr);
• (xi) Compositions consisting essentially of 91 to 52 weight percent of 3-ethoxy-perfluoro (2-methylhexane) and 9 to 48 weight percent of p-chlorobenzotrifluoride boiling at 126.8 to 127.8 ° C at approximately 1 bar (760 Torr) ;
• (xii) compositions consisting essentially of 83 to 36 weight percent of 3-ethoxy-perfluoro (2-methylhexane) and 17 to 64 weight percent of n-butyl acetate boiling at 117.6 to 118.6 ° C at about 1 bar (760 Torr) ;
• (xiii) compositions consisting essentially of 73 to 23 weight percent 3-ethoxy-perfluoro (2-methylhexane) and 27 to 77 weight percent isobutyl acetate boiling at 112.2 to 113.2 ° C at about 1 bar (760 torr);
• (xiv) compositions consisting essentially of 80 to 31% by weight of 3-ethoxy-perfluoro (2-methylhexane) and 20 to 69% by weight of n-propyl-n-propionate, which at 115.7 to 116.7 ° C at about 1 bar ( 760 Torr);
• (xv) compositions consisting essentially of 73 to 24 weight percent of 3-ethoxy-perfluoro (2-methylhexane) and 27 to 76 weight percent of methyl isobutyl ketone boiling at 110.9 to 111.9 ° C at about 1 bar (760 Torr);
• (xvi) compositions consisting essentially of 96 to 69 weight percent 3-ethoxy-perfluoro (2-methylhexane) and 4 to 31 weight percent 2-heptanone boiling at 127.7 to 128.7 ° C at about 1 bar (760 torr) ;
• (xvii) compositions consisting essentially of 99.9 to 75 weight percent of 3-Ethyoxyperfluor (2-methylhexane) and 0.1 to 25 weight percent diethylene glycol dimethyl ether (glyme), which at 128.9 to 129.9 ° C at about 1 bar (760 Torr) boil;
• (xviii) compositions consisting essentially of 96 to 67 weight percent 3-ethoxy-perfluoro (2-methylhexane) and 4 to 33 weight percent octamethyltrisiloxane boiling at 127.4 to 128.4 ° C at about 1 bar (760 torr);

Preferably, the azeotrope-like compositions are homogeneous, ie they form under Raumbe conditions, ie room temperature and air pressure, a single phase. Also, the azeotrope-like compositions are non-flammable ie they have a flash point above 100 ° F (38 ° C) or most preferably no flash point.

The similar azeotropelike Compositions are prepared by mixing the desired amounts of hydrofluoroether, of organic solvent and any other minor components such as surfactants Help conventional Mixing devices prepared.

method

Especially can the azeotrope-like compositions according to the invention in cleaning operations, heat transfer operations, as Coolant, as a reaction medium, as a blowing agent and as a coating liquid be used.

Cleaning, water displacement process

The Cleaning process according to the invention can by contacting a contaminated substrate with a the azeotrope-like invention Compositions until the contaminants dissolved on the substrate, dispersed or displaced in or by the azeotrope-like composition, and subsequent removal (for example, by rinsing the Substrate with fresh, uncontaminated azeotrope-like Composition or by removing a substrate in one Azeotropelike Composition is immersed, from the bath and allow that the contaminated azeotrope-like Composition drains from the substrate) of the azeotrope-like Composition that solved the, dispersed or displaced Contains pollution, performed by the substrate become. The azeotrope-like Composition can be either in the vapor or in the liquid state (or both) and any known technique for "contacting" a substrate can be used. For example, the liquid azeotrope-like Sprayed onto the substrate or applied with a brush be, the vaporous Azeotropelike Composition can about that Substrate may be blown or the substrate may either be in one vaporous or liquid Azeotropelike Be dipped in the composition. Elevated temperatures, ultrasonic energy and / or stirring can be used to facilitate cleaning. Various solvent cleaning techniques by B.N. Ellis in Cleaning and Contamination of Electronics Components and Assemblies (Cleaning and Contamination of Electronic Components and structures) Electrochemical Publications Limited, Ayr, Scotland, Pages 182-94 (1986).

Either Organic as well as inorganic substrates may be purified by the methods of the invention become. Representative Examples of the substrates include metals, ceramics, glass, Silicon wafers, polymers such as: polycarbonate, polystyrene and acrylonitrile butadiene styrene copolymer, natural Fibers (and derived materials) such as: cotton, silk, linen, Wool, ramie; Fur; Leather and suede; Synthetic fiber (and of it derived materials) such as: polyester, rayon, acrylic fibers, nylon, Polyolefin, acetates, triacetates and mixtures thereof; substances which is a mixture of natural and synthetic fibers; and compositions of the above materials. The procedure is for precision cleaning electronic components (e.g., printed circuits), optical or magnetic media and medical devices and medical articles like syringes, surgical equipment, implantable devices and prostheses particularly useful.

The Cleaning process according to the invention can to solve or removing most of the dirt from the surface of a Substrate can be used. For example, materials such as light hydrocarbon contaminants, higher molecular hydrocarbon contaminants such as mineral oils, fats, Cutting and punching oils and waxes, fluorocarbon contaminants such as perfluoropolyethers, Bromotrifluoroethylene oligomers (gyroscope fluids) and chlorotrifluoroethylene oligomers (hydraulic fluids, lubricants), silicone oils and fats, fluxes, particulate Fabrics and other contaminants used in precision, electronic, metal cleaning and cleaning medical devices be found, removed. The procedure is for removal hydrocarbon contaminants (especially light hydrocarbon oils), fluorocarbon contaminants, particulate Fabrics and water (as in the next Section).

To displace or remove water from substrate surfaces, the cleaning method of the present invention, as described in U.S. Patent No. 5,125,978 (Flynn et al.), May be preferably accomplished by contacting the surface of an article with an azeotrope-like composition nonionic fluoroaliphatic surfactant. The wet article is dipped in and stirred in the liquid azeotrope-like composition, the displaced water is separated from the azeotrope-like composition, and the resulting anhydrous article is removed from the liquid azeotrope-like composition. Further description of the method and articles which can be treated are found in U.S. Patent No. 5,125,978, and the method can also be practiced as described in U.S. Patent No. 3,903,012 (Brandreth).

The Azeotrope-like according to the invention Compositions are also for the extraction useful. Here, cleaning involves removing contaminants (e.g. Greasing, guards, oils or other solvents) by loosening or displace these materials of substances (e.g., foods, cosmetics, pharmaceutical products).

coating process

The similar azeotropelike Compositions can in coating deposition applications where the Azeotropelike Composition as a carrier for a Coating material works to deposit the material on the surface allow the substrate. The invention thus also provides a coating composition comprising the azeotrope-like Composition and a coating material and a method for depositing a coating on a substrate surface below Using the azeotrope-like Composition. The method includes the step of giving up on at least a part of at least one surface of a Substrate of a coating of a liquid coating composition comprising (a) an azeotrope-like Composition and (b) at least one coating material, the in the azeotrope-like Composition soluble or dispersible. The coating composition may be of the Further one or more additives (e.g., surfactants, colorants, Stabilizers, antioxidants and flame retardants). Preferably, the method further comprises the step of removing the azeotrope-like Composition of the deposited coating e.g. by permission evaporation (by use of, for example, heat or vacuum still supported can be).

The Coating materials deposited by the process can, include pigments, lubricants, stabilizers, adhesives, antioxidants, Dyes, polymers, pharmaceuticals, release agents and inorganic Oxides and combinations thereof. Preferred materials include Perfluoropolyether, hydrocarbon and silicon lubricant; amorphous copolymers of tetrafluoroethylene; polytetrafluoroethylene and combinations thereof. Representative examples of materials suitable for use in the process include titanium dioxide, Iron oxides, magnesium oxide, perfluoropolyethers, polysiloxanes, stearic acid, acrylic adhesives, Polytetrafluoroethylene, amorphous copolymers of tetrafluoroethylene and combinations thereof. Any of the above (for cleaning applications) described substrates can by the method according to the invention be coated. The process can be used for coating magnetic hard disks or electrical connectors with perfluoropolyether lubricants or medical devices with Silicone lubricants are particularly useful.

To the To form a coating composition, the components of the composition (i.e. the azeotrope-like Composition, coating material (s) and any (s) used additive (s)) by any conventional means Mixed technique for the loosening, Dispersing or emulsifying coating agents used is, e.g. by mechanical stirring, Ultrasonic stirring and manual stirring, be combined. The azeotrope-like Composition and / the coating material (s) can in any relationship, depending on the desired Thickness of the coating to be combined, the coating material (s) However, in most applications it is preferable to set / 0.1 to about 10 weight percent of the coating composition represents.

Of the Deposit process according to the invention can be achieved by applying the coating composition to a substrate by any conventional Technology performed become. For example, the composition may be on the substrate applied with a brush or sprayed (e.g., as an aerosol) or the substrate can be spun on. The substrate is preferred applied by immersion in the composition. The immersion can take place at any suitable temperature and for a useful Time span continued become. Is the substrate a tube, such as a catheter, and it is desirable to ensure that the composition coats the lumen wall, so it may be beneficial the composition by applying negative pressure in the lumen implicate.

To Applying a coating to a substrate can be azeotrope-like Composition of the deposited coating by evaporation be removed. If desired, The evaporation rate can be increased by applying negative pressure or lighter Heat to be accelerated. The coating may be any suitable one Thickness and in practice the thickness is determined by factors like the viscosity of the coating material, the temperature at which the coating is applied, and the extraction rate (if immersion applied is determined.

Heat transfer process

similar azeotropelike Compositions can also as heat transfer fluids used in heat transfer operations be where the heat transfer fluid Thermal energy (i.e., heat), either directly or indirectly can. The direct heat transfer (sometimes called "direct Contact heat transfer "is called) refers to a heat transfer process, in which a heat transfer fluid Heat directly (i.e., by conduction and / or convection) and / or from a heat source by direct contacting the fluid with the heat source to a fluid. Examples of direct heat transfer include immersion cooling electrical components and cooling an internal combustion engine.

indirect heat transfer refers to a heat transfer process, at the heat transfer fluid (sometimes referred to as "working fluid") heat to and / or from a heat source conducts, without bringing the fluid directly into contact with the heat source. Examples of indirect heat transfer include: cooling, Air conditioning and / or heating (e.g., using heat pumps) operations as in buildings, for example, Vehicles and stationary machines are used. At a embodiment For example, the present invention provides a method of transmission of heat comprising applying an azeotropic composition of the invention as a secondary Loop coolant. In this embodiment offers the secondary Loop coolant (i.e., liquid Fluid with a wide temperature range) means for transferring of heat between the heat source (i.e., the one to be cooled Subject) and the primary Loop coolant (i.e., a low-boiling fluid, the heat by expansion to absorbs a gas and heat by condensing to a liquid, typically condensed by use of a compressor) Examples of devices, in which the azeotropic invention Composition useful may include, but are not limited to, centrifugal coolers, refrigerators / freezers in the household, air conditioners for Vehicles, refrigerated Transport vehicles, heat pumps, Food refrigeration equipment for supermarkets and showcases and cold stores.

at indirect heat transfer processes can be lubricants be incorporated there into the working fluid, where moving Parts occur to ensure that the moving parts (e.g., pumps and valves) continue working for long periods of time. Such lubricants should a good heat and hydrolysis and have at least a partial solubility in the fluid. Examples of suitable lubricants include mineral oils, fatty esters, highly halogenated oils such as chlorotrifluoroethylene-containing polymers and synthetic lubricants such as alkylene oxide polymers.

reaction medium

The Azeotrope-like according to the invention Compositions are also known as reaction media for a series various reactions for preparing an organic compound useful. In particular, the azeotrope-like compositions in comparison with 3-ethoxyperfluoro (2-methylhexane), when they are the only one solvent used, an improved solvent power. These azeotrope-like compositions can higher for replacement boiling chlorofluorocarbons and chlorofluorocarbons which have been shown to be the ozone layer in the stratosphere to damage. The specific dissolving power of Reaction medium can be selected by appropriately selecting the organic solvent in the azeotrope-like Composition are tailored specifically. That allows that Choose an azeotrope-like Composition, which is a better solvent for the reactants as for the desired one represents organic compound and so easy separation of the Reactants of the desired allowed organic compound (which in the preparation of polymers is particularly important). This can not be flammable or poorly flammable azeotrope-like Low toxicity compounds that are an extensive series different solubility parameters have to be used. The reaction media can additionally Compounds that participate in the reaction include binding an organic compound, but substantially inert to the azeotrope-like composition such as catalysts, initiators, radical scavengers, precipitation aids, chain terminators and chain transfer agents.

The azeotrope-like compositions can be used as reaction media for a wide variety of organic reactions. Such reactions include radical chain polymerization, condensation reactions, oxidation and reduction reactions, radical addition reactions, nucleophile addition reactions, electrophile addition reactions, and nucleophile and electrophile substitution reactions. The organic reactions may be of the type requiring a catalyst or initiator, which may be the free radical type (ie, with the aid of an oxido-reduction mechanism), the cationic type, or the anionic type. The azeotrope-like compositions are particularly suitable for use in organic reactions involving one or more reactions which are fluorochemical compounds, for such compounds have excellent solubility in these compositions. According to the invention, the azeotrope-like compositions can be used as the reaction medium, in particular as the liquid solvent, in the free radical polymerization of a fluorochemical monomer (eg C ₄ F ₉ SO ₂ N (CH ₃ ) C ₂ H ₄ OC (O) CH = CH ₂ ) be used. The fluorochemical monomer can be copolymerized with an ethylenically unsaturated monomer that is free of fluorine (eg, C ₄ H ₉ OC (O) CH = CH ₂ ). Further descriptions of suitable reactants, monomers, catalysts, initiators and reaction conditions can be found in published PCT patent application WO 99/16809.

The Objects and advantages of this invention will become apparent through the following examples further illustrated.

EXAMPLES

The Preparation, identification and testing of the azeotrope-like compounds according to the invention Compositions will be described in more detail in the following examples.

Preparation of 3-ethoxyperfluoro (2-methylhexane)

3-Ethoxyperfluoro (2-methylhexane), nC ₃ F ₇ CF (OC ₂ H ₅ ) CF (CF ₃ ) ₂ used to prepare the azeotrope-like compositions and azeotropes of this invention was synthesized as follows.

Into a dry 600 milliliter Parr reactor were charged 36.3 grams (0.625 mole) of anhydrous potassium fluoride and 108 grams of anhydrous diglyme (diethylene glycol dimethyl ether). Potassium fluoride was prepared by spray drying, stored at 125 ° C and ground just prior to use. The reactor contents were cooled with dry ice, then 125 grams (0.52 moles) of nC ₃ F ₇ COF (about 90 percent pure) were added. When the reactor reached a temperature of 52 ° C and a pressure of 5.6 bar (4190 Torr), 101.5 grams (0.68 moles) of CF ₂ = CFCF ₃ (hexafluoropropylene) at 70 ° C and in a pressure range of 2.25-6.2 bar (1690-4640 torr) over a period of about 3 hours, followed by a 2 hour hold at 70 ° C. The reactor and its contents were then cooled to room temperature, the reactor was opened and an additional 1.5 grams of potassium fluoride was added along with 14.5 grams (0.016 mole) of ADOGEN ^™ 464 surfactant (as a 50 percent solution of solids in glyme). and 119.2 grams (0.77 mol) of diethyl sulfate. (ADOGEN ^™ 464 surfactant, available from Witco Corp., Oleo / Surfactant Group, Greenwich, CT) is a quaternary tri (octyldecyl) monomethyl ammonium chloride, 90 percent active; in this experiment, the ADOGEN ^™ 464 was diluted with anhydrous glyme and freed by vacuum fractionation to a concentration of 50% by weight in glyme from the alcohol solvent). The Parr reactor was then resealed tightly and heated to 52 ° C for three days with maximum stirring. The reactor was then pressurized with 60 grams of 45 weight percent aqueous potassium hydroxide and 50 grams of deionized water, again sealed, and heated to 85 ° C for 1½ hours. The reaction was allowed to cool overnight, the reactor was vented and its contents transferred to a flask for distillation. 235.2 grams of product were recovered, representing a 96.9 percent yield based on the nC ₃ F ₇ COF loading. Percent purity was 88.7 percent based on analysis by gas chromatography.

The recovered crude product was fractionated in a 10-tray jacketed vacuum Oldershaw column, washed with water and dried over anhydrous magnesium sulfate. A portion of the distilled and washed product was weighed accurately as it was loaded into an NMR tube and was charged with a known amount of 1,4-bis (trifluoromethyl) benzene ( _p -HFX) for use as a cross-integration or internal standard Mistake. Thereafter, a 1H-NMR spectrum of 400 MHz (# h56881.401) and a 19F-NMR spectrum of 376 MHz (# 56881, 402) were measured at room temperature using a Varian UNITYplus 400 FT NMR spectrometer at room temperature. This method of preparation allowed the p-HFX to be either (1) an internal standard for measuring absolute weight percent concentrations more specifically Components or (2) as a cross-integration standard to facilitate cross-correlation of the various fluorine and proton signal intensities for evaluating the total sample composition.

The Results of Proton and Fluorine NMR Cross Integration Determination are shown below in TABLE 1:

TABLE 1

The results from the NMR analysis show that the washed distillate contains 99.86% nC ₃ F ₇ CF (OC ₂ H ₅ ) CF (CF ₃ ) ₂ , the desired product.

Analysis of several other nC ₃ F ₇ CF (OC ₂ H ₅ ) CF (CF ₃ ) ₂ preparations performed during essentially the same synthesis and purification operations showed purities, in percent, of 99.71, 99, 89 and 99.96 percent.

Examples 1-18 and Comparative Example C1

In Examples 1-18, the azeotropes of this invention were originally identified by screening mixtures of 3-ethoxyperfluoro (2-methylhexane) ie, nC ₃ F ₇ CF (OC ₂ H ₅ ) CF (CF ₃ ) ₂ and various organic solvents. Unless otherwise stated, the organic solvents used to prepare the azeotrope-like compositions described in these examples were purchased commercially from Aldrich Chemical Company, Milwaukee, WI. In Comparative Example C1, the 3-ethoxyperfluoro (2-methylhexane) was judged as such as a pure solvent without added organic solvent.

Mixtures of 3-ethoxyperfluoro (2-methylhexane) and organic solvent were evaluated to determine the composition of the azeotrope. Mixtures of 3-ethoxyperfluoro (2-methylhexane) and the organic solvent of interest were prepared and stored at laboratory ambient pressure of 0.97-0.99 bar (725-739 torr) in a concentric tube distillation column (model 9333, ex Ace Glass, Vineland, NJ, available). The distillation process was allowed to equilibrate under total reflux for at least 60 minutes. For each distillation, six consecutive distillate samples of approximately 5 volume percent each of the total liquid charge were withdrawn while the column operated at a liquid reflux ratio of 20 to 1. The compositions of the distillate samples were then analyzed using a HP-5890 Series II Plus gas chromatograph with a 30 meter HP-5 capillary column (stationary phase of 5-percent cross-linked phenylmethyl silicone rubber, available from Hewlett Packard Co.), NUKOL ^™ (ex Supelco Inc Bellefonte, PA) or STABILWAXDA ^™ (available from Altech Associates, Deerfield, IL) and a flame ionization detector. The boiling points of the distillate were measured by means of a thermocouple, which had an accuracy of about 1 ° C. The data on the composition and the respective boiling points are listed in TABLE 2.

The 3-ethoxyperfluoro (2-methylhexane) and its azeotropes were also tested for flammability by placing a small aliquot of each azeotrope in an open aluminum dish and holding a flame source in contact with the vapor of the azeotrope over the dish. Flame propagation across the vapor indicated that the azeotrope was flammable. The flammability data are in TA BLLE 2 listed.

Examples 19-36 and Comparative Example C2

The azeotrope-like compositions of Examples 1-18 containing 3-ethoxyperfluoro (2-methylhexane) were tested for their ability to solubilize normal hydrocarbons of increasing molecular weight according to a test method similar to that described in US Pat Patent No. 5,275,669 (Van Der Puy et al.). In accordance with this test procedure, 0.5 to 2 ml of the azeotrope-like test composition was placed in a vial. An equal volume of n-octane (nC ₈ H ₁₈ ) was then added to the same vial. The vial was tightly closed by closing the lid and the vial was shaken to mix the two components. When undiluted settling for several minutes resulted in a turbid mixture or split phase, the azeotrope-like composition was given a SLK ("most soluble hydrocarbon") rating of <8. When a clear solution was obtained, the Repeated test, replacing n-octane with n-nonane (nC ₉ H ₂₀ ). When a cloudy mixture or phase separation occurred, the azeotrope-like composition was assigned an SLK rating of 8. The test was consistently higher homologous n-alkanes to n-heenicosane (nC ₂₁ H ₄₄ ) until a cloudy mixture or phase separation took place The assigned SLK rating corresponded to the length of the carbon chain of the largest soluble n-alkane, which was a homogeneous solution in equal volumes For example, when n-decane (nC ₁₀ H ₂₂ ) became the largest soluble n-alk, the SLK rating became however, n-undecane (nC ₁₁ H ₂₄ ), causing phase separation, was recorded as 10. The hydrocarbon solubilities in the azeotrope-like compositions were measured at both room temperature and the boiling points of the azeotrope-like compositions, the latter being accomplished by immersing each test vial in a constant temperature bath for equilibration. The results are shown in Table 3.

The Data in Table 3 show that the hydrocarbyl alkanes are in the Azeotrope-like according to the invention Compositions are extremely soluble, especially at their boiling point, making the azeotrope-like Composition excellent solvents for the cleaning process of the invention represent. These compositions are also used as solvents for the Depositing hydrocarbon coatings, e.g. coatings of lubricants, to be effective on substrate surfaces.

Examples 37-54

The Percentage ranges of the azeotrope-like compositions of the invention were determined by determining the boiling points of test compositions by Mixing 3-ethoxyperfluoro (2-methylhexane) with various organic solvents made with the help of an echinodermoscope or boiling point apparatus (specifically, model MBP-100 available from Cal-Glass for Research, Inc., Costa Mesa, CA available is identified). To perform this test, the lower-boiling components became the test compositions (typically an amount of 25 to 30 ml) of the boiling point apparatus added, heated, and down to its boiling point (typically allowed to equilibrate for about 30 minutes). After equilibration the boiling point was recorded, a 1.0 ml aliquot of the higher boiling component was added to the apparatus and the new composition thus formed was allowed to equilibrate for 30 minutes left, at which time the boiling point was recorded. The test was basically continued as described above, with additives of 1.0 ml of the higher boiling component every 30 minutes to the test mixture, to 15 to 20 ml of the higher boiling component had been added. The presence of a Azeotrope was then noted when the test mixture was lower Boiling point was found to be the boiling point of lower boiling Component of the test mixture. The corresponding to the above-mentioned boiling points Compositions were determined. The composition (weight percent) of the organic test solvent in the composition then became graphic as a function of boiling point recorded. By examining each graphic record were areas of azeotrope-like Composition identified (on a weight percent basis), at temperatures within about 1 ° C of the respective azeotropic boiling point boiled (with the azeotrope defined as this composition the lowest boiling point resulted).

The resulting regions of the azeotrope-like composition and the corresponding boiling temperature range (1 ° C from the azeotropic boiling temperature, 0.4 ° C from the azeotropic boiling temperature for ISOPAR ^™ G) are shown in Table 4. The organic solvents are referred to as "solvents" and 3-ethoxyperfluoro (2-methylhexane) is referred to as "ethers". All boiling tests were carried out under a pressure of 1 bar (760 ± 1 Torr) at which pure 3-ethoxyperfluoro (2-methylhexane) boils at about 130 ° C.

The Data in TABLE 4 show that azeotropic compositions that 3-ethoxyperfluoro (2-methylhexane) and a number of different organic solvent contain, can be formulated the one big Composition range but low boiling point range exhibit.

Claims (18)

Azeotrope-like composition comprising: a) 3-ethoxyperfluoro (2-methylhexane); and b) organic solvent; wherein the composition is selected from the group consisting of: (i) compositions consisting essentially of 86 to 41% by weight of 3-ethoxyperfluoro (2-methylhexane) and 14 to 59% by weight of n-octane present at 115, 5 to 116.5 ° C at 1 bar (760 Torr) boiling; (ii) Compositions consisting essentially of 79 to 32 wt .-% of 3-ethoxyperfluoro (2-methylhexane) and 21 to 68 wt .-% of 1,3-dimethylcyclohexane, which at 112.0 to 113.0 ° C at 1 boiling point (760 torr); and (iii) compositions consisting essentially of 99.9 to 89% by weight of 3-ethoxyperfluoro (2-methylhexane) and 0.1 to 11% by weight of ISOPAR ^™ G, which is a mixture of high purity C ₁₀ -C ₁₁ isoparaffinic hydrocarbons boiling at 129.7 to 130.1 ° C at 1 bar (760 torr). An azeotrope-like composition according to claim 1, comprising: a) 3-ethoxyperfluoro (2-methylhexane); and b) organic solvent; wherein the composition is an azeotrope selected from the group consisting of: (i) a composition consisting essentially of 71.6 weight percent of 3-ethoxyperfluoro (2-methylhexane) and 28.4 weight percent of n-octane, the boiling at 113.1 ° C at 0.976 bar (731.9 Torr); (ii) a composition consisting essentially of 65.1% by weight of 3-ethoxyperfluoro (2-methylhexane) and 34.9% by weight of 1,3-dimethylcyclohexane, which at 109.7 ° C at 0.975 bar (731 5 Torr) and (iii) a composition consisting essentially of 95.4 weight percent 3-ethoxyperfluoro (2-methylhexane) and 4.6 weight percent ISOPAR ^™ G, which is a mixture of high purity C ₁₀ -C _{11 is} isoparaffinic hydrocarbons boiling at 126.7 ° C at 0.972 bar (729.3 Torr). Azeotropelike Composition comprising: a) 3-ethoxyperfluoro (2-methylhexane) and b) organic solvent; in which the composition is selected from the group consisting of: (I) Compositions consisting essentially of 74 to 20% by weight 3-ethoxyperfluoro (2-methylhexane) and 26 to 80 wt .-% 1-chloro-n-pentane, which at 103.8 to 104.8 ° C at 1 bar (760 Torr) boil; (ii) Compositions consisting essentially from 89 to 55% by weight of 3-ethoxyperfluoro (2-methylhexane) and 11 to 45 wt .-% 1-chloro-n-hexane, which at 120.1 to 121.1 ° C at 1 bar (760 torr) boiling and (iii) compositions consisting in Substantially from 98 to 68 wt .-% of 3-ethoxyperfluoro (2-methylhexane) and 2 to 32 wt .-% 1-chloro-n-heptane, which at 128.0 to 129.0 ° C at 1 bar (760 Torr) boiling. Azeotropelike A composition according to claim 3, comprising: a) 3-ethoxyperfluoro (2-methylhexane) and b) organic solvent; in which the composition is an azeotrope selected from the group consisting out: (i) a composition consisting essentially of 53.4% by weight of 3-ethoxyperfluoro (2-methylhexane) and 46.6% by weight of 1-chloro-n-pentane, at 102.9 ° C at 0.968 bar (725.9 Torr) boiling; (ii) a composition consisting essentially of 74.8 wt .-% 3-ethoxyperfluoro (2-methylhexane) and 25.2% by weight of 1-chloro-n-hexane, which at 118.3 ° C at 0.979 bar (734.3 Torr) boils and (iii) a composition consisting essentially from 93.1% by weight of 3-ethoxyperfluoro (2-methylhexane) and 6.9% by weight of 1-chloro-n-heptane, at 126 ° C boiling at 0.985 bar (738.4 torr). Azeotrope-like composition comprising: a) 3-ethoxyperfluoro (2-methylhexane) and b) organic solvent; wherein the composition is selected from the group consisting of: (i) compositions consisting essentially of 76 to 24% by weight of 3-ethoxyperfluoro (2-methylhexane) and 24 to 76% by weight of toluene present at 105.1 to Boiling at 106.1 ° C at 1 bar (760 torr); (ii) Compositions consisting essentially of 91 to 58% by weight of 3-ethoxyperfluoro (2-methylhexane) and 9 to 42% by weight of m-xylene, which at 122.3 to 123.3 ° C at 1 bar ( 760 Torr) and (iii) Compositions consisting essentially of 96 to 65% by weight of 3-ethoxyperfluoro (2-methylhexane) and 4 to 35% by weight of α-pinene which are dissolved at 127.1 to 128.1 ° C. at 1 bar ( 760 torr), (iv) compositions consisting essentially of 99.7 to 77% by weight of 3-ethoxyperfluoro (2-methylhexane) and 0.3 to 23% by weight of β-pinene at 128.8 to And (v) compositions consisting essentially of 91 to 52% by weight of 3-ethoxyperfluoro (2-methylhexane) and 9 to 48% by weight of p-chlorobenzotrifluoride, the at 126.8 to 127.8 ° C at 1 bar (760 Torr) boiling. Azeotropelike A composition according to claim 5, comprising: a) 3-ethoxyperfluoro (2-methylhexane) and b) organic solvent; in which the composition is an azeotrope selected from the group consisting out: (i) a composition consisting essentially of 57.7% by weight of 3-ethoxyperfluoro (2-methylhexane) and 42.3% by weight of toluene, at 103.0 ° C at 0.977 bar (732.5 Torr) boiling; (ii) a composition consisting essentially of 80.8 wt .-% 3-ethoxyperfluoro (2-methylhexane) and 19.2% by weight of m-xylene at 119.7 ° C at 0.979 bar (734.3 torr). boils and (iii) a composition consisting essentially from 88.5 wt .-% 3-ethoxyperfluoro (2-methylhexane) and 11.5 wt .-% α-pinene, the at 125.3 ° C at 0.979 bar (734 Torr) boiling; (iv) a composition consisting essentially of 94.2 wt .-% 3-ethoxyperfluoro (2-methylhexane) and 5.8% by weight of β-pinene, at 126.7 ° C boiling at 0.977 bar (732.7 Torr) and (v) a composition consisting essentially of 75.7 wt .-% 3-ethoxyperfluoro (2-methylhexane) and 24.3% by weight of p-chlorobenzotrifluoride, which at 124 ° C at 0.971 bar (728.1 Torr) boils. Azeotropelike Composition comprising: a) 3-ethoxyperfluoro (2-methylhexane) and b) organic solvent; in which the composition is selected from the group consisting of: (I) Compositions consisting essentially of 83 to 36% by weight 3-ethoxyperfluoro (2-methylhexane) and 17 to 64% by weight of n-butyl acetate, at 117.6 to 118.6 ° C boil at 1 bar (760 torr); (ii) compositions consisting essentially from 73 to 23% by weight of 3-ethoxyperfluoro (2-methylhexane) and 27 to 77 wt .-% isobutyl acetate, which at 112.2 to 113.2 ° C at 1 bar (760 torr) boiling and (iii) compositions consisting in Substantially from 80 to 31 wt .-% 3-Ethoxyperfluor (2-methylhexane) and 20 to 69 wt .-% of n-propyl n-propionate, which at 115.7 to 116.7 ° C at 1 bar (760 Torr) boiling. Azeotropelike A composition according to claim 7, comprising: a) 3-ethoxyperfluoro (2-methylhexane) and b) organic solvent; in which the composition is an azeotrope selected from the group consisting out: (i) a composition consisting essentially of 67.9% by weight of 3-ethoxyperfluoro (2-methylhexane) and 32.1% by weight of n-butyl acetate, at 116 ° C at 0.976 bar (732 Torr) boiling; (ii) a composition consisting essentially of 56.8% by weight of 3-ethoxyperfluoro (2-methylhexane) and 43.2% by weight of isobutyl acetate dissolved at 110.1 ° C. at 0.976 bar (732.2 torr). boils and (iii) a composition consisting essentially of 63.8% by weight of 3-ethoxyperfluoro (2-methylhexane) and 36.2% by weight n-propyl n-propionate, which at 114.2 ° C at 0.976 bar (731.9 Torr) boils. Azeotropelike Composition comprising: a) 3-ethoxyperfluoro (2-methylhexane) and b) organic solvent; in which the composition is selected from the group consisting of: (I) Compositions consisting essentially of 73 to 24% by weight 3-ethoxyperfluoro (2-methylhexane) and 27 to 76% by weight of methyl isobutyl ketone, that at 110.9 to 111.9 ° C boiling at 1 bar (760 torr); (ii) compositions consisting essentially from 96 to 69% by weight of 3-ethoxyperfluoro (2-methylhexane) and 4 to 31 wt .-% 2-heptanone, which at 127.7 to 128.7 ° C at 1 bar (760 Torr) boiling. An azeotrope-like composition according to claim 9, comprising: a) 3-ethoxyperfluoro (2-methylhexane) and b) organic solvent; wherein the composition is an azeotrope selected from the group consisting of: (i) a composition consisting essentially of 59.1% by weight of 3-ethoxyperfluoro (2-methylhexane) and 40.9% by weight of methyl isobutyl ketone present at 109 , 2 ° C at 0.977 bar (732.9 Torr) boiling; (ii) a composition consisting essentially of 89.6% by weight of 3-ethoxyperfluoro (2-methylhexane) and 10.4% by weight of 2-heptanone boiling at 126 ° C at 0.984 bar (738.2 Torr). Azeotropelike Composition comprising: a) 3-ethoxyperfluoro (2-methylhexane) and b) organic solvent; in which the composition selected from the group consisting essentially from 99.9 to 75% by weight of 3-ethoxyperfluoro (2-methylhexane) and 0.1 to 25 wt .-% diethylene glycol dimethyl ether, which at 128.9 to 129.9 ° C at 1 bar (760 Torr) boiling. Azeotropelike A composition according to claim 11, comprising: a) 3-ethoxyperfluoro (2-methylhexane) and b) organic solvent; in which the composition is an azeotrope selected from the group consisting essentially 93.6% by weight of 3-ethoxyperfluoro (2-methylhexane) and 6.4 wt .-% diethylene glycol dimethyl ether, which at 126.9 ° C at 0.985 bar (738.6 Torr) boiling. Azeotropelike Composition comprising: a) 3-ethoxyperfluoro (2-methylhexane) and b) organic solvent; in which the composition selected from the group consisting essentially from 96 to 67% by weight of 3-ethoxyperfluoro (2-methylhexane) and 4 to 33 Wt .-% octamethyltrisiloxane boiling at 127.4 ° C to 128.4 ° C at 1 bar (760 Torr). Azeotropelike A composition according to claim 13, comprising: a) 3-ethoxyperfluoro (2-methylhexane) and b) organic solvent; in which the composition is an azeotrope selected from the group consisting consisting of a composition consisting essentially of 87.1% by weight 3-ethoxyperfluoro (2-methylhexane) and 12.9 wt% octamethyltrisiloxane, that at 125.2 ° C at 0.978 bar (733.7 Torr) boiling. Procedure for depositing a coating on a substrate surface, comprising the step of giving up on at least a part of at least one surface the substrate of a liquid Coating composition comprising: (a) an azeotrope-like A composition according to any one of claims 1, 3, 5, 7, 9, 11 or 13; and (b) at least one coating material used in the similar azeotropelike Composition soluble or dispersible. Coating composition consisting essentially from an azeotrope-like one A composition according to any one of claims 1, 3, 5, 7, 9, 11 or 13 and a coating material. Procedure for removing contaminants from the surface of a substrate comprising Step of contacting the substrate with one or more the azeotrope-like Compositions according to any one of claims 1, 3, 5, 7, 9, 11 or 13, until the soiling in or through the azeotrope-like (s) Composition solved, dispersed or displaced and removing these dissolved, dispersed or displaced contaminants containing azeotrope-like Composition from the surface of the substrate. Procedure for the heat transfer, wherein one or more of the azeotrope-like compositions according to one of the claims 1, 3, 5, 7, 9, 11 or 13 as a heat transfer fluid be used.